Phase change solid imaging material

ABSTRACT

A solubilizing agent and a compound made by reacting selected nucleophiles, including fatty acid reactants and amines with an isocyanate are disclosed. The addition of the isocyanate and the different nucleophiles will create a di-urethane tetra-amide solubilizing agent product. The polyamide-solubilizing agent is useful as an ingredient in a phase change solid imaging material and as carrier compositions used to make phase change ink jet inks.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to resins or waxes made by reactingisocyanates with selected nucleophiles such as fatty acid reactants andamines. The nucleophiles are used to achieve certain desirableproperties in urethane polyamide resins. The present invention alsorelates to solid imaging materials used in the rapid prototypingindustry, as well as to phase change ink compositions, both generallyand in specific compositions, containing such resins and/or waxes. Stillfurther, the present invention relates to the process of using suchphase change compositions containing such resins and/or waxes in aprinting device.

2. Description of the Relevant Art

In general, phase change materials or inks (sometimes referred to as"hot melt inks") are in the solid phase at ambient temperature, butexist in the liquid phase at the elevated operating temperature of anink jet printing device. At the jet operating temperature, droplets ofliquid ink are ejected from the printing device and, when the inkdroplets contact the surface of the printing media, they quicklysolidify to form a predetermined pattern of solidified ink drops. Phasechange inks have also been investigated for use in other printingtechnologies such as gravure printing as referenced in U.S. Pat. No.5,496,879 and German patent publications DE 4205636AL and DE 4205713ALassigned to Siegwert Farbenfabrik Keller, Dr. Rung and Co.

Phase change inks for color printing generally comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. Preferably, a colored phase change ink will beformed by combining the above-described ink carrier composition withcompatible subtractive primary colorants. Subtractive primary coloredphase change inks can comprise four component dyes, namely, cyan,magenta, yellow and black. U.S. Pat. Nos. 4,889,506; 4,889,761; and5,372,852 teach that the subtractive primary colorants employedtypically may comprise dyes from the classes of Color Index (C.I.)Solvent Dyes, Disperse Dyes, modified Acid and Direct Dyes, and alimited number of Basic Dyes. The colorants can also include pigments asexemplified in U.S. Pat. No. 5,221,335, assigned to CoatesElectrographics Ltd. U.S. Pat. No. 5,621,022 assigned to Tektronix,Inc., is directed to the use of a specific class of polymeric dyes inphase change ink compositions.

Phase change inks are desirable for ink jet printers since they remainin a solid phase at room temperature during shipping, long-term storage,and the like. Also, the problems associated with nozzle clogging due toink evaporation are largely eliminated, thereby improving thereliability of ink jet printing. Furthermore, in the above-noted priorart phase change ink jet printers where the ink droplets are applieddirectly onto the printing medium, the droplets solidify immediatelyupon contact with the substrate, migration of ink along the printingmedium is prevented and dot quality is improved. More recently, the useof phase change solid imaging material with ink jet print heads haspermitted the rapid prototyping and manufacturing industry to increasespeed, reduce costs and improve part quality. This is also true of theprocesses and solid imaging compositions described herein.

In addition to the above-referenced U.S. patents, many other patentsdescribe materials for use in phase change ink jet inks. Somerepresentative examples include U.S. Pat. Nos. 3,653,932; 4,390,369;4,484,948; 4,684,956; 4,851,045; 4,889,560; 5,006,170; and 5,151,120; aswell as EP Application Nos. 0187352 and 0206286. These materials caninclude paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide-containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters are an example) andmany synthetic resins, oligomers, polymers and co-polymers.

Separately, PCT patent application WO 94/14902, which was published onJul. 7,1994 and is assigned to Coates Brothers PLC, teaches a hot meltink containing a colorant and, as a vehicle for the hot melt ink anoligourethane having a melting point of at least 65° C. and obtained byreacting an aliphatic or aromatic diisocyanate with at least astoichiometric amount of either: (I) a monohydric alcohol component; or(ii) a monohydric alcohol component followed by another differentalcohol component; or (iii) a monohydric alcohol component, followed bya dihydric alcohol component, followed by a monohydric alcoholcomponent.

This PCT patent application defines the monohydric alcohol component aseither a monohydric aliphatic alcohol (e.g. C₁ to C₂₂ alcohols), anetherified dihydric aliphatic alcohol [e.g. propylene glycol methylether (PGME), dipropylene glycol methyl ether (DPGME), ethylene glycolbutyl ether (EGBE), diethylene glycol butyl ether (DPGBE), tripropyleneglycol butyl ether (PGBE) and propylene glycol phenyl ether (PPL)];esterified dihydric aliphatic alcohol [e.g. the esterifying acid may bean ethylenically unsaturated acid (such as acrylic acid or methacrylicacid), thereby introducing ethylenic unsaturation into the oligourethaneand rendering it suitable for eventual further additional polymerization(curing) after having been applied to a substrate by hot-melt printing],or dihydric polyakylene glycol. This PCT application further defined thedihydric alcohol component as a dihydric aliphatic alcohol or a dihydricpolyalkylene glycol [e.g. ethylene glycol, polyethylene glycol (PEG1500), polypropylene glycol (PPG 750), 1000 and 1500), trimethyleneglycol, dipropylene glycol, methylpropanediol and 1.6-hexanediol].

Another PCT patent application, WO 97/12003 also assigned to CoatesBrothers PLC, discloses hot melt ink jet base materials that areurethane-amide reaction products obtained from the reaction ofisocyanates with one or more functional amides. The urethane-amides areintended to have improved compatibility with viscosity modifyingadditives.

Also, PCT Patent Application WO 94/04619, assigned to the GeneralElectric Company, teaches the use of ionomeric materials in combinationwith image forming agents to form a hot melt ink jet ink. The ionomericmaterials can include many different types of copolymeric or polymericionomers, including carboxyl-functional polyurethanes prepared from adiol or polyol and a hydroxyl acid. Many other carrier materials andcolorants for the image forming agent of the invention are included inthis PCT application.

There is still a need for new materials for novel and differentapplications of phase change materials. There is also a need forrelatively low viscosity resins, including nonpolymeric resins, andwaxes designed for phase change ink jet and other forms of phase changematerial printing and rapid prototyping applications. These needs aresolved by the present invention by providing a means to create asolubilizing agent that is an isocyanate-derived material for specificapplications.

BRIEF SUMMARY OF THE INVENTION

It is an aspect of the present invention that a urethane compoundcomprising the reaction product of selected isocyanates with selectedfatty acid reactants and selected amines are obtained.

It is another aspect of the present invention that a urethane compoundcomprising the reaction product of selected isocyanates with selectedamines or mixtures of selected amines and fatty acid reactants obtained.

It is still another aspect of the present invention that a phase changesolid imaging material or a phase change ink carrier composition whichis an admixture of a viscosity modifying agent, a tackifier, a urethanepolyamide compound, and a polyamide resin is obtained.

It is still a further aspect of the present invention that a phasechange ink composition comprising an admixture of (a) a phase changecarrier composition containing at least one isocyanate-derived resin orwax, and (b) a phase change ink compatible colorant is obtained.

It is a feature of the present invention that the amide isocyanatederived resin product of the selected isocyanates with selected fattyacid reactants and selected amines or mixtures of selected aminesobviates the need for the use of a separate plasticizer when the resinis employed in a solid imaging material or polyamide ink formulationbecause the resulting material or ink is sufficiently malleable andductile on its own.

It is an advantage of the present invention that the isocyanate-derivedresins can be design engineered to obtain desired properties forspecific printing or rapid prototyping platforms and architectures.

It is another advantage of the present invention that the amideisocyanate-derived resins are very pure, being free of salts and otherinsoluble contaminants.

It is still another advantage of the present invention that the amideisocyanate-derived resins can be used in combination with other phasechange solid imaging material or polyamide materials to obtain inkcompositions and rapid prototyping solid imaging materials that displayimproved yield stress over prior art ink compositions.

It is yet another advantage of the present invention that theisocyanate-derived resins have low viscosity.

It is yet a further advantage of the present invention that the lowviscosity polyamide isocyanate-derived resins permit the use of highermolecular weight polyamide resins in combination with a tackifier and aviscosity modifying agent to form a phase change solid imaging materialor phase change ink carrier composition.

These and other aspects, features and advantages are obtained by the useof reaction products of selected isocyanates with selected amines andselected fatty acids to produce amide isocyanate-derived resins suitablefor use in phase change solid imaging materials and inks that may beemployed in rapid prototyping or printing applications.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term "isocyanate-derived resin" as used in the present specificationand claims is defined as any monomeric, oligomeric or non-polymericresinous material derived from the reaction of mono-, di-, orpoly-isocyanates with suitable nucleophilic molecules.

The term "isocyanate-derived wax" as used in the present specificationand claims is defined as any crystalline or semicrystalline waxymaterial derived from the reaction of a fatty isocyanate with a suitablenucleophile, or the reaction of a fatty nucleophile with a suitableisocyanate, or the reaction of a fatty nucleophile with a fattyisocyanate.

Any suitable reaction condition for making urethane or urea compounds bycondensing alcohols and/or amines with isocyanates may be employed inthe practice of the present invention. Preferably, the reaction iscarried out at elevated temperatures (e.g. about 60° C. to about 160°C.) in the presence of a urethane reaction catalyst such as dibutyltindilaurate, bismuth tris-neodecanoate, cobalt benzoate, lithium acetate,stannous octoate or triethylamine. The reaction conditions preferablyare conducted in an inert atmosphere, such as argon or nitrogen gas orother suitable atmosphere, to prevent oxidizing or yellowing thereaction products and to prevent undesirable side reactions. The moleratio of reactants is adjusted so that the isocyanate functionalitiesare completely consumed in the reaction with a slight molar excess ofalcohol or amine typically remaining. Conceptually the reactants can beadded together in any order and/or added to the reaction as physicalmixtures. However, in the preferred embodiments of the invention,reaction conditions and the order of the addition of reactants arecarefully controlled for several reasons. First, reaction conditions andreactant additions are chosen to provide a controlled exothermicreaction. Secondly, when reacting mixtures of alcohols and/or amineswith diisocyanates such as isophorone diisocyanate (IPDI), the order ofaddition of the isocyanate and the different nucleophiles to thereaction is chosen to tailor the distribution of diurethane molecules,and/or mixed urethane/urea molecules, and/or diurea molecules in thefinal resin. When doing this, the different reactivities to isocyanatesof alcohols versus amines are employed, as are the differentreactivities of the two separate isocyanate groups on IPDI. See J. H.Saunders and K. C. Frisch's "Polyurethanes Part I, Chemistry" publishedby Interscience of New York, N.Y. in 1962 and Olin Chemicals' Luxate® Misophorone diisocyanate technical product information sheet whichprovide further explanation of this chemistry. This control of thereaction conditions and order of addition of the reactants is done tospecifically tailor or customize the different types of molecularspecies in the finished resin so that the resin will:

(1) have a controlled viscosity that is designed for a specificapplication, (2) have a controlled glass transition temperature and/ormelting point, and (3) have consistent properties from batch to batch.

The isocyanate-derived resins from these reactions are generallytransparent solids having melting points in the range of about 20° C. toabout 150° C., viscosities in the range of about 10 cPs to about 5000cPs at 150° C. and T_(g) 's of about -30° C. to about 100° C. Theisocyanate-derived waxes from these reactions are generally opaque waxysolids having sharp melting points in the range from about 20° C. toabout 130° C. and viscosities of from about 1 cPs to about 25 cPs at140° C. The isocyanate-derived resins and waxes display properties suchthat the higher the T_(g) and the melting point, the higher is theviscosity. While the structural activity relationships are not fullyunderstood, it is known that the T_(g) of the isocyanate-derived resinsis controlled by the proper choice of the mixture of nucleophiles in thereaction as illustrated in Table 1 below. Varying one or more of thereadily available commodity chemicals used as chemical precursors willpermit custom-tailoring of the properties of the isocyanate-derivedresin and wax materials.

Table 1 illustrates the difference in physical properties of resins thatcan be obtained by mixing both functionality and molecular shape andsize.

                  TABLE 1                                                         ______________________________________                                        Mixtures of Abietic Alcohol and Stearyl Amine, Reacted with IPDI                Alcohol/Amine Ratio                                                                             T.sub.g 's/Melting Point/Viscosity                        ______________________________________                                        100% Alcohol    40° C./72-76° C./4079 cPs @ 140° C.                       75% Alcohol/25% Amine 23° C./68-87° C./315                     cPs @ 140° C.                                            62.5% Alcohol/37.5% Amine 17° C./68-89° C./2759 cPs @                         140° C.                                                  50% Alcohol/50% Amine 16° C./73-110° C./15.7 cPs @                            140° C.                                                ______________________________________                                    

Preferred alcohols to react with difunctional and higher isocyanates tomake the isocyanate-derived waxes and resins of this invention includeany monohydric alcohol. For instance, the monohydric alcohol could beany aliphatic alcohol [e.g., a C₁ -C₂₂ or higher linear alcohol, anybranched alcohol or any cyclic aliphatic alcohol such as methanol,ethanol, (n- and iso)-propanol, (n-, iso-, t-) butanol, (n-, iso-, t-,and the like) pentanol, (n-, iso-, t-, and the like) hexanol, (n-, iso-,t-, and the like) octanol, (n-, iso-, t-, and the like) nonanol, (n- andbranched) decanols, (n- and branched) undecanols, (n- and brancheddodecanols, (n- and branched) hexadecanols, (n- and branched)octadecanols, 3-cyclohexy-1-propanol, 2-cyclohexyl-1-ethanol,cyclohexylmethanol, cyclohexanol, 4-methyl cyclohexanol,4-ethylcyclohexanol, 4-t-butylcyclohexanol, and the like]; analiphatic/aromatic alcohol [e.g., benzyl alcohol, octyl, nonyl, anddodecylphenol alkoxylates of octyl, nonyl, and dodecylphenol alkoxylatesof octyl, nonyl, and dodecylphenol, and alkoxyphenol]; aromatic alcoholssuch as phenol, naphthol, and the like, and their derivatives; fusedring alcohols (e.g., rosin alcohols, hydroabietyl alcohol, cholesterol,vitamin E, and the like) and other suitable alcohols (e.g.,N,N-dimethyl-N-ethanolamine, stearamide-monoethanolamine,tripropyleneglycol monomethylether, hydroxybutanone, menthol, isobomeol,terpineol, 12-hydroxy stearyl stearamide, and the like). It will beobvious to those skilled in the art that small amounts (on a molarbasis) of polyols could also be incorporated into the reaction mixtureto produce oligomeric species in the resins if so desired The preferredalcohols are hydroabietyl alcohol, octylphenol ethoxylate and octadecylalcohol.

Preferred amines to react with difunctional and higher isocyanates tomake the isocyanate-derived waxes and resins of this invention includeany monofunctional amine, with the exception of tertiary amines void ofother nucleophilic functional groups (e.g., triethylamine). Forinstance, the monoamine could be any aliphatic primary or secondaryamine (e.g., a C₁ -C₂₂ or higher linear amine, any branched amine or anycyclic aliphatic amine) such as methyl amine, ethyl amine, (n- andiso-)propyl amine, (n-, iso-, and t-) butyl amine, (n-, iso-, t-, andthe like) pentyl amine, (n-, iso-, t-, and the like) hexyl amine, (n-,iso- t-, and the like) octyl amine, (n-, iso-, t-, and the like) nonylamine, (n- and branched) decyl amine, (n- and branched) undecyl amines,(n- and branched) dodecyl amines, (n- and branched) hexadecyl amines,(n- and branched) dodecyl amines, dimethyl amine, diethyl amine, di(n-and iso-)propyl amines, di(n-, iso-, t-) butyl amine, di(n-, iso-, t-,and the like) pentyl amine, di(n-, iso-, t-, and the like) hexyl amine,di(n-, iso-, t-, and the like) cyclohexyl amine, di(n-, iso-, t-, andthe like) heptyl amine, di(n-, iso-, t-, and the like) octyl amine,di(n-, iso-, t-, and the like) decyl amine, di(n-, iso-, t-, and thelike) dodecyl amine, di(n-, iso-, t-, and the like) octadecyl amine,cyclohexyl amine, 2,3-dimethyl-1- cyclohexylamine, piperidine,pyrrolidine, and the like; an aliphatic/aromatic amine (e.g., benzylamine or analogues with longer or additional alkyl chains); aromaticamines such as aniline, anisidine, and the like; fused ring amines suchas rosin amine, dehydroabietyl amine, dihydroabietyl amine, hydroabietylamine, and the like; and miscellaneous amines (e.g., adamantyl amine,isonipecotamide, polyoxyalkylenemonoamines, such as M- series Jeffaminesavailable commercially from Huntsman Chemical Company of Austin, Tex.;3,3'-diamino-N-methyidipropylamine, and the like. It will be obvious tothose skilled in the art that small amounts (on a molar basis) ofpolyamines could also be incorporated into the reaction mixture toproduce oligomeric species in the resins if so desired. The preferredamine is octadecyl amine.

Preferred alcohols to react with monofunctional isocyanates to make theisocyanate-derived waxes and resins of this invention include anymonohydric alcohol. For instance, the monohydric alcohol could be anyaliphatic alcohol [e.g., a C₁ -C₂₂ or higher linear alcohol, anybranched alcohol or any cyclic aliphatic alcohol such as methanol,ethanol, (n- and iso-) propanol, (n-, iso-, and t-) butanol, (n-, iso-,t-, and the like) pentanol, (n-, iso-, t-, and the like) hexanol, (n-,iso-, t-, and the like) octanol, (n-, iso-, t-, and the like) nonanol,(n- and branched) decanols, (n- and branched) undecanols, (n- andbranched) dodecanols, (n- and branched) hexadecanols, (n- and branched)octadecanols, 3-cyclohexyl-1-propanol, 2-cyclohexyl-1- ethanol,cyclohexylmethanol, cyclohexanol, 4-methyl cyclohexanol, 4-ethylcyclohexanol, 4-t-butylcyclohexanol, and the like]; analiphatic/aromatic alcohol (e.g., benzyl alcohol, octyl, nonyl, anddodecylphenol alkoxylates or octyl, nonyl, and dodecylphenol,alkoxyphenol); aromatic alcohols such as phenol, naphthol, and the like,and their derivatives; fused ring alcohols (e.g., rosin alcohols,hydroabietyl alcohol, cholesterol, vitamin E, and the like) and othersuitable alcohols (e.g., N,N-dimethyl-N-ethanolamine,stearamide-monoethanolamine, tripropyleneglycol monomethylether,hydroxybutanone, menthol, isoborneol, terpineol, 12-hydroxy stearylstearamide, and the like), as well as multifunctional alcohols such asethylene glycol, diethylene glycol, triethylene glycol,dimethylolpropionic acid, sucrose, polytetramethylene glycol (MW<-3000),polypropylene glycol (MW<-3000), polyester polyols (MW<-3000),polyethylene glycol (MW<-3000), pentaerythritol, triethanol amine,glycerin, 1,6-hexanediol, N-methyl-N,N-diethanol amine, trimethylolpropane, N,N,N', N'-tetrakis(2- hydroxypropyl) ethylenediamine, and thelike. The preferred alcohol is octadecanol.

Preferred amines to react with monofunctional isocyanates to make theisocyanate-derived waxes and resins of this invention include anymonofunctional amine, with the exception of tertiary amines void ofother nucleophilic functional groups (e.g., triethylamine). Forinstance, the monoamine could be any aliphatic primary or secondaryamine (e. g., a C₁ -C₂₂ or higher linear amine, any branched amine orany cyclic aliphatic amine such as methyl amine, ethyl amine, (n- andiso-) propyl amine, (n-, iso-, and t-) butyl amine, (n-, iso-, t-, andthe like) pentyl amine, (n-, iso-, t-, and the like) hexyl amine, (n-,iso-, t-, and the like) octyl amine, (n-, iso-, t-, and the like) nonylamine, (n- and branched) decyl amine, (n- and branched) undecyl amine,(n- and branched) octadecyl amine, (n- and branched) hexadecyl amine,(n- and branched) dodecyl amine, dimethyl amine, diethyl amine, di(n-,and iso-) propyl amine, di(n-, iso-, t-) butyl amine, di(n-, iso-, t-,and the like) pentyl amine, di(n-, iso-, t-, and the like) hexyl amine,di(n-, iso-, t-, and the like) cyclohexyl amine, di(n-, iso-, t-, andthe like) heptyl amine, di(n-, iso-, t-, and the like) octyl amine,di(n-, iso-, t-, and the like) decyl amine, di(n-, iso-, t-, and thelike) octadecyl amine, di(n-, iso-, t-, and the like) dodecyl amine,cyclohexyl amine, 2,3-dimethyl-1-cyclohexylamine, piperidine,pyrrolidine, and the like); any aliphatic/aromatic amines (e.g., benzylamine or analogues with longer or additional alkyl chains); aromaticamines such as aniline, anisidine, and the like; fused ring amines suchas rosin amine, dehydroabietyl amine, dihydroabietyl amine, hydroabietylamine, and the like; and miscellaneous amines (e.g., adamantyl amine,isonipecotamide, polyoxyalkylenemono-, di-, or triamines, such as M-,D-, and T- series Jeffamines available commercially from HuntsmanChemical Company of Austin, Tex.; 3,3'-diamino-N-methyl-dipropylamine,and the like, as well as multifunctional amines such as polyethyleneimine; ethylene diamine; hexamethylene diamine; isomers ofcyclohexyldiamines; 1,3- pentadiamine; 1,12-dodecanediamine;3-dimethylaminopropylamine; 4,7,10-trioxa-1,13- tridecanediamine;diethylene triamine; 3,3-diamino-N- methyldipropylamine;tris(2-aminoethyl) amine, and the like. The preferred amine isoctadecylamine. In solid imaging applications monoamines, such as2-hydroxy ethylamine, and diamines, such as ethylenediamine,1,3-propylenediamine; 2-butyl-2 ethyl-1,5-pentylenediamine; and1,2-diaminocyclohexane are especially useful.

Additionally, hydroxyl/amino containing compounds can be employed (withdi- and higher functionality isocyanates taking advantage of thedifference in reactivity of the amine over the hydroxyl group, or withmonoisocyanates reacting with the amine preferentially or with both theamine and the hydroxyl groups). Examples of this include ethanolamine,diethanolamine, and the like.

Additionally amides or other nucleophile containing compounds can bereacted with the isocyanates (mono, di, and the like). Some examplesinclude: urea, oleamide, stearamide, or the like.

Preferred precursors to the isocyanate-derived resins and waxes of thepresent invention include mono-, di- and other poly- isocyanates.Examples of monoisocyanates include octadecylisocyanate;octylisocyanate; butyl and t-butylisocyanate; cyclohexyl isocyanate;adamantyl isocyanate; ethylisocyanatoacetate; ethoxycarbonylisocyanate;phenylisocyanate; alphamethylbenzyl isocyanate; 2-phenylcyclopropylisocyanate; benzylisocyanate; 2-ethylphenylisocyanate;benzoylisocyanate; meta and paratolylisocyanate; 2-, 3-, or4-nitrophenylisocyanates; 2- ethoxyphenyl isocyanate; 3-methoxyphenylisocyanate; 4- methoxyphenylisocyanate; ethyl 4-isocyanatobenzoate; 2,6-dimethylphenylisocyanate; 1-naphthylisocyanate; (naphthyl)ethylisocyantes; and the like. Examples of diisocyanates includeisophorone diisocyanate (IPDI); toluene diisocyanate (TDI);diphenylmethane-4,4'-diisocyanate (MDI); hydrogenateddiphenylmethane-4,4'-diisocyanate (H₁₂ MDI); tetra-methyl xylenediisocyanate (TMXDI); hexamethylene-1,6-diisocyanate (HDI);hexamethylene-1,6-diisocyanate; napthylene-1,5-diisocyanate;3,3'-dimethoxy-4,4'-biphenyldiisocyanate; 3,3'-dimethyl-4,4'-bimethyl-4,4'-biphenyldiisocyanate; phenylene diisocyanate;4,4'-biphenyldiisocyanate; trimethylhexamethylene diisocyanate;tetramethylene xylene diisocyanate; 4,4'-methylenebis(2,6-diethylphenylisocyanate); 1,12-diisocyanatododecane;1,5-diisocyanato-2-methylpentane; 1,4-diisocyanatobutane; andcyclohexylene diisocyanate and its isomers; uretidione dimers of HDI;and the like. Examples of triisocyanates or their equivalents includethe trimethylolpropane trimer of TDI, and the like, isocyanurate trimersof TDI, HDI, IPDI, and the like, and biuret trimers of TDI, HDI, IPDI,and the like. Examples of higher isocyanate functionalities includecopolymers of TDI/HDI, and the like, as well as MDI oligomers.

Phase change materials of this invention contain a phase change carriersystem or composition. The phase change carrier composition is generallydesigned for use in either a direct printing mode or use in an indirector offset printing transfer system. In the direct printing mode, thephase change carrier composition is generally made up of one or morechemicals that provide the necessary properties to allow the phasechange ink (1) to be applied in a thin film of uniform thickness on thefinal receiving substrate when cooled to the ambient temperature afterprinting directly to the substrate; (2) to be ductile while retainingsufficient flexibility so that the applied image on the substrate willnot fracture upon bending; and (3) to possess a high degree oflightness, chroma, transparency and thermal stability. In an offsetprinting transfer or indirect printing mode, the phase change carriercomposition is designed to possess not only the above mentionedproperties, but certain fluidic and mechanical properties necessary foruse in such a system, as described in U.S. Pat. No. 5,389,958 which ishereby incorporated by reference in pertinent part. The phase changeinks and solid imaging material of the current invention incorporateisocyanate-derived waxes and isocyanate-derived resins as all or as partof the carrier composition or imaging material and can be a supplementalingredient or supplemental ingredients to what is currently available asthe existing phase change carrier or imaging material composition. Theisocyanate-derived materials of the current invention are tailored tohave the desirable properties mentioned above when used in the carriercomposition of the inks or in the solid damaging material of the presentinvention by varying one or more of the readily available commoditychemical precursors.

The phase change carrier compositions or solid imaging materialcompositions of the current invention may be used in combination withconventional phase change ink colorant materials such as Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acid and Direct Dyes, BasicDyes, Sulphur Dyes, Vat Dyes, and/or polymeric dyes such as thosedisclosed in U.S. Pat. No. 5,621,022, and/or pigments. They may also beused in combination with the isocyanate-derived colored resins of U.S.Pat. No. 5,780,528 to produce a phase change ink.

Prior art phase change inks for use in direct and indirect transferprinting systems from which the carrier compositions may be useful insolid imaging applications are described in U.S. Pat. Nos. 4,889,560 and5,372,852. These inks consist of a phase change ink carrier compositioncomprising one or more fatty amide-containing materials, usuallyconsisting of a mono-amide wax and a tetra-amide resin, one or moretackifiers, one or more plasticizers and one or more antioxidants, incombination with compatible colorants. A preferred tetra-amide resin isa dimer acid based tetra-amide that is the reaction product of dimeracid, ethylene diamine, and stearic acid. A preferred mono-amide isstearyl stearamide. A preferred tackifier resin is a glycerol ester ofhydrogenated abietic (rosin) acid and a preferred antioxidant is thatprovided by Uniroyal Chemical Company under the tradename Naugard 524.The isocyanate-derived resins and/or isocyanate-derived waxes of thepresent invention replace one or more of the ingredients in the abovephase change ink carrier composition, or the inks or solid imagingmaterials can have all of the above ingredients replaced by theisocyanate-derived resins and/or waxes of the present invention. Onedesirable characteristic of the formulations used in solid imaging forrapid prototyping and manufacturing applications is a high yield stresswhich provides toughness, as opposed to the low yield stress desired forformulations used in ink carrier compositions where flexibility isrequired.

Suitable classes of tackifiers that may be employed, especially withsolid imaging materials include rosin ester, rosin carbamate, glycerinrosin ester, hydrogenated pentaerythritol ester, hydrogenated glycerinester, modified tall oil rosin, polymerized rosin, aromatic hydrocarbonrosin, and aliphatic hydrocarbon rosin. Preferred tackifiers, especiallywith solid imaging materials, include butyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methylcarbamate;hexyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methylcarbamate; octyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methylcarbamate; dodecyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methylcarbamate; and octadecyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methylcarbamate.

Suitable viscosity modifiers or viscosity modifying agents in solidimaging materials include urethane wax, amide wax, alkyl wax andcombinations thereof. A preferred viscosity modifying agent is a linearalkyl urethane or carbamate. The linear alkyl carbamate is selected fromthe group consisting of octadecyl octadecyl carbamate; dodecyl octadecylcarbamate; hexadecyl octadecyl carbamate; and hexyl octadecyl carbamate.

The solubilizing agents useful for polyamide resins in both solid inkand solid imaging materials are a diurethane monoamide, a diurethanetri-amide, a diurethane tetra-amide and combinations thereof.

The following examples of the synthesis of urethane tetra-amides andsolid imaging material are presented to illustrate the scope of theinvention and to be illustrative of solid imaging materials, as well asphase change ink formulations, that can be employed successfully using aurethane tetra-amide, without any intent to limit the invention to thespecific materials, process or structure employed.

In the following examples, the synthesis of urethane tetra-amide wasperformed in a glass kettle equipped with heating metal, temperaturecontroller, mechanical stirrer, water condenser and nitrogen gas inlet.The completeness of the reactions was followed by using a Model 1760FTIR Spectrophotometer available commercially from Perkin-Elmer ofNorwalk, Conn. The UV-Visible spectra of the products were recordedusing a Shimazu Model UV-1201 spectrophotometer. The melting point ofthe products were determined using a Model DSC 550 differential scanningcalorimeter available commercially from Instrument SpecialistIncorporated. The viscosity of the obtained products was measured usinga high temperature Brookfield Model DV-II+ viscometer.

EXAMPLE 1

About 300 grams of 12-hydroxystearic acid available commercially fromCasChem of Bayonne, N.J., about 286 grams of stearic acid availablecommercially from Adrich Chemicals of Milwaukee, Wis. and about 61 gramsof ethylenediamine commercially available from Aldrich Chemicals wereadded and stirred into the mixture in the reaction kettle. The reactionwas heated to about 110° C. for two hours. The reaction temperature wasincreased to about 180° C. for an additional two hours. The reactiontemperature was decreased to about 80° C. About 84 grams of1,6-dicyanatohexane commercially available as Desmodur H from BayerCorporation of Pittsburgh, Pa., and about 0.1 grams of dibutyltindilaurate also commercially available from Aldrich Chemicals were thenadded into the reaction mixture. The temperature of the reaction wasraised to about 140° C. and stirred for two hours. After being cooled toroom temperature, a translucent tan solid product was obtained having amelting point at about 45° C. and viscosity of about 61.8 cPs at 150° C.

EXAMPLE 2

About 300 grams of 12-hydroxystearic acid available commercially fromCasChem of Bayonne, N.J., about 286 grams of stearic acid availablecommercially from Adrich Chemicals of Milwaukee, Wis., and about 61grams of ethylenediamine commercially available from Aldrich Chemicalswere added and stirred into the mixture in the reaction kettle. Thereaction was heated to about 110° C. for two hours. The reactiontemperature was increased to about 180° C. for an additional two hours.The reaction temperature was decreased to about 80° C. About 111 gramsof isophorone diisocyanate commercially available as Desmodur I fromBayer Corporation of Pittsburgh, Pa., and about 0.1 grams of dibutyltindilaurate also commercially available from Aldrich Chemicals were thenadded into the reaction mixture. The temperature of the reaction wasraised to about 140° C. and stirred for two hours. After being cooled toroom temperature, a translucent tan solid product was obtained having amelting point at about 133° C. and viscosity of about 87.1 cPs at 150°C.

EXAMPLE 3

About 300 grams of 12-hydroxystearic acid available commercially fromCasChem of Bayonne, N.J., about 286 grams of stearic acid availablecommercially from Adrich Chemicals of Milwaukee, Wis., and about 61grams of ethylenediamine commercially available from Aldrich Chemicalswere added and stirred into the mixture in the reaction kettle. Thereaction was heated to about 110° C. for two hours. The reactiontemperature was increased to about 180° C. for an additional two hours.The reaction temperature was decreased to about 80° C. About 125 gramsof 4,4-methylene bis(phenylisocyanate) commercially available asDesmodur I from Bayer Corporation of Pittsburgh, Pa., and about 0.1grams of dibutyltin dilaurate also commercially available from AldrichChemicals were then added into the reaction mixture. The temperature ofthe reaction was raised to about 140° C. and stirred for two hours.After being cooled to room temperature, a translucent tan solid productwas obtained having a melting point at about 132° C. and viscosity ofabout 156 cPs at 150° C.

EXAMPLE 4

About 300 grams of 12-hydroxystearic acid available commercially fromCasChem of Bayonne, N.J., about 286 grams of stearic acid availablecommercially from Adrich Chemicals of Milwaukee, Wis., and about 74grams of 1,3-propylenediamine also available commercially from AldrichChemicals were added into the reaction kettle. The reaction was heatedto about 110° C. for two hours then increased to about 180° C. for anadditional two hours. The reaction temperature was decreased to about80° C. About 111 grams of isophorone diisocyanate available commerciallyas Desmodur I from Bayer Corporation of Pittsburgh, Pa., and about 0.1grams of dibutyltin dilaurate also commercially available from AldrichChemicals were then added into the reaction mixture. The temperature ofthe reaction was raised to about 140° C. and stirred for two hours.After being cooled to room temperature, a translucent tan solid productwas obtained having a melting point at about 64° C. and viscosity ofabout 274 cPs at about 135° C.

EXAMPLE 5

About 300 grams of 12-hydroxystearic acid available commercially fromCasChem of Bayonne, N.J., about 286 grams of stearic acid availablecommercially from Adrich Chemicals of Milwaukee, Wis., and about 190grams of 2-butyl-2-ethyl-1,5-pentylenediamine also availablecommercially from Aldrich Chemicals were added into the reaction kettle.The reaction was heated to about 110° C. for two hours and thenincreased to about 180° C. for an additional two hours. The reactiontemperature was decreased to about 80° C. About 111 grams of isophoronediisocyanate available commercially as Desmodur I from Bayer Corporationof Pittsburgh, Pa., and about 0.1 grams of dibutyltin dilaurate alsocommercially available from Aldrich Chemicals were then added into thereaction mixture. The temperature of the reaction was raised to about140° C. and stirred for two hours. After being cooled to roomtemperature, a translucent tan solid product was obtained having amelting point at about 46° C. and viscosity of about 267 cPs at about135° C.

EXAMPLE 6

About 300 grams of 12-hydroxystearic acid available commercially fromCasChem of Bayonne, N.J., about 286 grams of stearic acid availablecommercially from Aldrich Chemicals of Milwaukee, Wis., and about 114grams of 1,2-diaminocyclohexane also available commercially from AldrichChemicals were added into the reaction kettle. The reaction was heatedto about 110° C. for two hours then increased to about 180° C. for anadditional two hours. The reaction temperature was decreased to about80° C. Then, about 111 grams of isophorone diisocyanate commerciallyavailable as Desmodur I from Bayer Corporation of Pittsburgh, Pa., andabout 0.1 grams of dibutyltin dilaurate also commercially available fromAldrich Chemicals were then added into the reaction mixture. Thetemperature of the reaction was raised to about 140° C. and stirred fortwo hours. After being cooled to room temperature, a translucent tansolid diurethane tetra-amide product was obtained having a melting pointat about 51° C. and viscosity of about 155 cPs at about 135° C.

EXAMPLE 7

About 300 grams of 12-hydroxystearic acid available commercially fromCasChem of Bayonne, N.J., about 286 grams of stearic acid availablecommercially from Adrich Chemicals of Milwaukee, Wis., and about 61grams of ethylenediamine also available commercially from AldrichChemicals were added into the reaction kettle. The reaction was heatedto about 110° C. for two hours then increased to about 180° C. for anadditional two hours. The reaction temperature was decreased to about80° C. About 552 grams of 12-hydroxystearyl-stearylamide availablecommercially from American Dye Source of Montreal, Canada, was added.Then, about 222 grams of isophorone diisocyanate commercially availableas Desmodur I from Bayer Corporation of Pittsburgh, Pa., and about 0.1grams of dibutyltin dilaurate also commercially available from AldrichChemicals were then added into the reaction mixture. The temperature ofthe reaction was raised to about 140° C. and stirred for two hours.After being cooled to room temperature, a translucent tan soliddiurethane tri-amide product was obtained having a melting point atabout 64° C. and viscosity of about 92 cPs at about 135° C.

EXAMPLE 8

About 300 grams of 12-hydroxystearic acid available commercially fromasChem of Bayonne, N.J., about 286 grams of stearic acid availablecommercially from Adrich Chemicals of Milwaukee, Wis., and about 61grams of ethylenediamine also available commercially from AldrichChemicals were added into the reaction kettle. The reaction was heatedto about 110° C. for two hours then increased to about 180° C. for anadditional two hours. The reaction temperature was decreased to about80° C. About 342 grams of 2-hydroxyethylstearylamide availablecommercially from American Dye Source of Montreal, Canada, was added.Then, about 222 grams of isophorone diisocyanate commercially availableas Desmodur I from Bayer Corporation of Pittsburgh, Pa., and about 0.1grams of dibutyltin dilaurate also commercially available from AldrichChemicals were then added into the reaction mixture. The temperature ofthe reaction was raised to about 140° C. and stirred for two hours.After being cooled to room temperature, a translucent tan soliddiurethane tri-amide product was obtained having a melting point atabout 17 ° C. and viscosity of about 39.3 cPs at about 135° C.

EXAMPLE 9

About 363 grams of 2-hydroxyethyl 12'-hydroxy stearamide availablecommercially as Paracin 220 from CasChem of Bayonne, N.J., was heated toabout 60° C. About 591 grams of 1-ocatadecylisocyanate commerciallyavailable from Bayer Corporation of Pittsburgh, Pa., and about 0.1 gramsof dibutyltin dilaurate also commercially available from AldrichChemicals were then added into the reaction mixture. The temperature ofthe reaction was raised to about 140° C. and stirred for two hours.After being cooled to room temperature, a translucent tan soliddiurethane mono-amide product was obtained having a melting point atabout 90° C. and viscosity of about 14.5 cPs at about 135° C.

EXAMPLE 10

About 342 grams of monoamide S acid available commercially from MonaIndustry of Patterson, N.J., was heated to about 60° C. About 295 gramsof 1-octadecylisocyanate commercially available from Bayer Corporationof Pittsburgh, Pa., and 0.1 grams of dibutyltin dilaurate alsocommercially available from Aldrich Chemicals were then added into thereaction mixture. The temperature of the reaction was raised to about140° C. and stirred for two hours. After being cooled to roomtemperature, a translucent tan solid monourethane mono-amide product wasobtained having a viscosity of about 9.4 cPs at about 135° C.

EXAMPLE 11

Solid Imaging Material Formulation Using Solubilizing Agent In a 200 mlglass beaker about 51 grams of hexadecyl, octadecyl carbamate, availablefrom ADS of Montreal, Canada; about 8 grams of hexyl, octadecylcarbamate, also available from ADS of Montreal, Canada; about 20 gramsof hexyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methylcarbamate; about 14 grams of the translucent tan solid product obtainedin Example 2; about 2.5 grams of Polyamide Resin 2942 available fromArizona Chemical; about 2.5 grams of Polyamide Resin 2614 available fromArizona Chemical; and about 2.0 grams of Irganox 1010 an anti-oxidantavailable commercially from Ciba Geigy were mixed together at atemperature of about 140° C. on a hot plate and then blended by stirringin a temperature controlled mantle at about 115° C. for about 1/2 hour.After stirring, the imaging material base was filtered through a 1micron Pall filter available from Pall Filters of East Hills, N.Y. At apressure of about five pounds per square inch, the filtered phase changematerial was poured into molds and allowed to solidify, forming disks ofsolid imaging material. The solid imaging material created employed thediurethane tetra-amide from Example 2 as a solubilizing agent, acarbamate viscosity modifier, and a tackifier that yielded a tough,flexible formulation suitable for solid imaging materials. The materialhad a viscosity at about 135° C. of about 12.5 cPs. The lrganox 1010anti-oxidant is used to suppress the thermal oxidation of the carbamate.

While the invention has been described above with reference to specificembodiments thereof, it is apparent that many changes, modifications andvariations can be made without departing from the inventive conceptdisclosed herein. For example, it should be noted where a urethanereaction product is obtained, a single alcohol precursor of multiplealcohol precursors may be used with an appropriate isocyanate as long asthe required stoichiometric ratio is maintained. Accordingly, it isintended to embrace all such changes modifications and variation thatfall within the spirit and broad scope of the appended claims. Allpatent applications, patents and other publications cited herein areincorporated by reference in their entirety.

What is claimed:
 1. A formulation for use in jetting from a print headcomprising:(a) a viscosity modifying agent; (b) a tackifier; (c) apolyamide resin; and (d) a solubilizing agent for the polyamide resin,the agent being selected from the group consisting of monourethanemonoamide a diurethane monoamide, a diurethane tri-amide, a diurethanetetra-amide and combinations thereof.
 2. A formulation according toclaim 1 wherein the viscosity modifying agent is selected from the groupconsisting of a urethane wax, an amide wax, alkyl wax and combinationsthereof.
 3. The formulation according to claims 2 wherein the urethanewax is a linear alkyl carbamate.
 4. The formulation according to claim 3wherein the linear alkyl carbamate is selected from the group consistingof octadecyl octadecyl carbamate; dodecyl octadecyl carbamate; hexadecyloctadecyl carbamate; and hexyl octadecyl carbamate.
 5. The formulationaccording to claim 1 wherein the tackifier is selected from the groupconsisting of a rosin carbamate, a rosin ester, glycerin rosin ester,hydrogenated pentaerythritol ester, hydrogenated glycerin ester,modified tall oil rosin, a polymerized rosin, an aromatic hydrocarbonrosin, an aliphatic hydrocarbon rosin.
 6. The formulation according toclaim 1 wherein the tackifier is a rosin carbamate tackifier selectedfrom the group consisting of butyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenantbrenyl)methoxy]carbonyl}amino)-14,4-trimethylcyclohexyl]methyl carbamate; hexyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy)carbonyl}amino)-14,4-trimethylcyclohexyl]methylcarbamate; octyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl]carbamate; dodecyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methylcarbamate; and octadecyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methy)carbamate.
 7. The formulation according to claim 1 wherein thesolubilizing agent is the reaction product of a fatty acid, an amine,and an isocyanate.
 8. The formulation according to claim 7 wherein thefatty acid is selected from the group consisting of a fatty acid, ahydroxy fatty acid, and combinations thereof.
 9. The formulationaccording to claim 7 wherein the reaction product further includes analcohol as an additional reactant.
 10. The formulation according toclaim 7 wherein the isocyanate is selected from the group consisting ofa monoisocyanate, a diisocyanate, a triisocyanate, a copolymer of adiisocyanate and a copolymer of a triisocyanate and combinationsthereof.
 11. The formulation according to claim 10 wherein theisocyanate is a diisocyanate selected from the group consisting of1,6-dicyanatohexane, isophorone diisocyanate, and 4,4'-methylenebis(phenylisocyanate).
 12. The formulation according to claim 7 whereinthe amine is a diamine.
 13. The formulation according to claim 12wherein the diamine is selected from the group consisting ofethylenediamine, 1,3-propylenediamine; 2-butyl-2ethyl-1.5-pentylenediamine; and 1,2-diaminocyclohexane.
 14. Theformulation according to claim 7 wherein the amine is a monoamine. 15.The formulation according to claim 14 above wherein the monoamine is2-hydroxy ethylamine.
 16. The formulation according to claim 7 whereinthe fatty acid reactant is selected from the group consisting of stearicacid, decanoic acid, myristic acid, and docasanic acid.
 17. Theformulation according to claim 2 wherein the urethane wax is thereaction product of a monohydric alcohol and amono-isocyanate.
 18. Theformulation according to claim 17 wherein the monohydric alcohol isselected from the group consisting of an aliphatic alcohol, analiphatic/aromatic alcohol, an aromatic alcohol, and a fused ringalcohol and combinations thereof.
 19. A solid imaging material for usein three-dimensional model rapid prototyping comprising:(a) a viscositymodifying agent; (b) a tackifier; (c) a polyamide resin; and (d) asolubilizing agent for the polyamide resin, the agent being a diurethanetetra-amide.
 20. The material according to claim 19 wherein theviscosity modifying agent is a urethane wax.
 21. The compound accordingto claim 20 wherein the urethane is a linear alkyl urethane wax.
 22. Thecompound according to claim 21 wherein the linear alkyl urethane isselected from the group consisting of octadecyl, octadecyl carbamate;dodecyl octadecyl carbamate; hexadecyl octadecyl carbamate; and hexyloctadecyl carbamate.
 23. The compound according to claim 19 wherein thetackifier is a rosin urethane wax.
 24. The compound according to claim19 wherein the tackifier is selected from the group consisting of butyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methylcarbamate; hexyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methylcarbamate; octyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methylcarbamate; dodecyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methylcarbamate; and octadecyl[3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methylcarbamate.
 25. The compound according to claim 19 wherein the diurethanetetra-amide is the reaction product of a fatty acid reactant, an amine,and an isocyanate.
 26. The reaction product according to claim 25wherein the isocyanate is selected from the group consisting of amonoisocyanate, a diisocyanate, a triisocyanate, a copolymer of atriisocyanate and a copolymer of a triisocyanate and combinationsthereof.
 27. The material according to claim 19 wherein the isocyanateis a diisocyanate selected from the group consisting of1,6-dicyanatohexane, isophorone diisocyanate, and 4,4'-methylenebis(phenylisocyanate).
 28. The material according to claim 19 whereinthe amine is a diamine.
 29. The material according to claim 28 whereinthe diamine is selected from the group consisting of ethylenediamine,1,3-propylenediamine; and 2-butyl-2-ethyl-1,5-pentylenediamine.
 30. Thematerial according to claim 25 wherein the fatty acid reactant isselected from the group consisting of stearic acid, decanoic acid,myristic acid, and docasanic acid.
 31. The material according to claim20 wherein the urethane wax is the reaction product of a monohydricalcohol and a mono-isocyanate.
 32. The formulation according to claim 31wherein the monohydric alcohol is selected from the group consisting ofan aliphatic alcohol, an aliphatic/aromatic alcohol, an aromaticalcohol, and a fused ring alcohol and combinations thereof.